CN107221654B - Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof - Google Patents

Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof Download PDF

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CN107221654B
CN107221654B CN201710376252.8A CN201710376252A CN107221654B CN 107221654 B CN107221654 B CN 107221654B CN 201710376252 A CN201710376252 A CN 201710376252A CN 107221654 B CN107221654 B CN 107221654B
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silicon
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surfactant
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马树华
李艳凯
龙志
徐鹏远
孙洋
张小康
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University of Jinan
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and a preparation method thereof, wherein the composite negative electrode material comprises nano silicon powder and SiOxA layer, carbon nanotubes, and a carbon shell formed by pyrolysis of a surfactant; the addition of the surfactant can effectively inhibit the agglomeration of the nano silicon particles, the carbon layer generated on the surface of the nano silicon particles during the high-temperature pyrolysis of the surfactant can improve the conductivity of the composite material, and the toughness and strength properties of different surfactant pyrolytic carbons are utilized to inhibit the volume effect in the process of silicon lithiation/delithiation; nanometer silica powder and SiOxThe layer, the carbon nano tube and the surfactant pyrolytic carbon jointly construct a three-dimensional porous nest-shaped structure in the silicon-carbon composite material; compared with the initial capacity, the capacity of the silicon-carbon composite negative electrode material prepared by the method has no attenuation after 500 cycles, and the silicon-carbon composite negative electrode material has high capacity and excellent cycle stability; the process method provided by the invention has the advantages of simple operation, low cost, large-scale production and the like.

Description

Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof
The technical field is as follows:
the invention relates to a three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and a preparation method thereof, belonging to the technical field of negative electrode materials of lithium ion batteries.
Background art:
lithium ion batteries have the advantages of high energy density, good safety, long cycle life, etc., have grown into novel energy storage and conversion devices, and have been widely used in the fields of portable electronic products, electric tools, electric vehicles, etc. The current commercialized lithium ion battery cathode material is mainly graphite, but the specific capacity is low, and meanwhile, potential safety hazards of forming lithium dendrites exist during overcharge, so that the requirements of electric automobiles, aerospace, large and medium-sized wind and light energy storage power stations and the like on high-performance lithium ion batteries cannot be further met.
The theoretical specific capacity of silicon in the currently known lithium storage materials is the highest (4200 mA h g)-1) And the lithium insertion potential of silicon is higher (> 0.2V vs. Li)+Li), good safety, abundant reserves and low production cost, and is the most potential next generation lithium ion battery cathode material. However, the silicon negative electrode material is accompanied by huge volume change of more than 300% in the charging and discharging process, and the generated mechanical stress can cause the crushing and pulverization of silicon particles, so that the capacity of the silicon-based material is rapidly attenuated; LiPF in conventional electrolytes6HF generated by the action of residual moisture reacts with silicon, a stable SEI film is difficult to form, and the coulombic efficiency and the capacity retention rate of the electrode are low; secondly, the conductivity of silicon is poor, and a high-conductivity material is required to be added when the silicon is used as an electrode material.
In order to solve the problems, researches at home and abroad mainly focus on reducing the volume effect of a silicon cathode, increasing the conductivity of a silicon material, exploring a novel electrolyte system and the like. The modification of the silicon negative electrode material can be summarized as the following aspects: firstly, the size of the silicon material is reduced to a nanometer level so as to effectively relieve the volume expansion effect of silicon, and based on the thought, the nanometer level materials such as hollow silicon nanoparticles, nanowires, nanotubes and the like are researched and prepared; secondly, preparing a porous silicon material, and relieving the volume effect of silicon in the electrochemical reaction by utilizing a pore channel structure in silicon particles, wherein the commonly used pore channel structure comprises micropores, mesopores, macropores and the like; and thirdly, the silicon-carbon composite material is prepared, the carbon material has certain mechanical strength, toughness and high conductivity, the conductivity of the material can be increased, the deformation and stress generated by silicon in the volume change process can be effectively restrained, absorbed and relieved, and the silicon-carbon composite material has a good effect of improving the cycle performance of the silicon electrode material.
The invention content is as follows:
the invention aims to provide a three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the three-dimensional porous nest-shaped silicon-carbon composite negative electrode material is characterized by comprising nano silicon powder and SiOxA layer, carbon nanotubes, and a carbon shell formed by pyrolysis of a surfactant; the silicon-carbon composite material contains 15-50 wt% of silicon and SiOxThe content of (1-10 wt.%), the content of carbon nano tube is 5-30 wt.%, and the content of surfactant pyrolytic carbon is 1-30 wt.%.
Preferably, the surfactant is one or more of an anionic surfactant such as a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type, a cationic surfactant such as an amine type, a quaternary ammonium type, and a heterocyclic type, a zwitterionic surfactant such as an amino acid type and a betaine type, or a nonionic surfactant such as a polyoxyethylene type and a polyhydric alcohol type.
Preferably, the carbon nanotube is one or two of a single-walled carbon nanotube and a multi-walled carbon nanotube, the typical tube diameter is 1-100 nm, and the length-diameter ratio is 1000: 1 or more.
Preferably, the particle size distribution of the nano silicon powder is in the range of 30-500 nm.
A preparation method of a three-dimensional porous nest-shaped silicon-carbon composite negative electrode material is characterized by comprising the following synthesis steps:
1) silicon/carbon nanotube/surfactant pretreatment: dispersing a surfactant in a solvent, adding nano silicon powder and carbon nano tubes, and carrying out ultrasonic stirring treatment to obtain a uniformly dispersed mixed solution;
2) preparation of silicon/carbon nanotube/surfactant precursor: transferring the mixed solution obtained by the treatment in the step 1) into a reaction kettle for hydrothermal reaction treatment;
3) silicon/SiOxPreparation of carbon nanotube/surfactant precursor: separating the solvent from the silicon/carbon nanotube/surfactant precursor obtained by the step 2) by using a rotary evaporator, and carrying out pre-oxidation treatment in a muffle furnace;
4) silicon/SiOxPreparing a/carbon nano tube/carbon composite negative electrode material: silicon/SiO treated by the step 3)xAnd pyrolyzing the carbon nanotube/surfactant precursor at high temperature under the protection of inert gas in a tube furnace.
Preferably, the solvent in the step 1) is one or more of deionized water, methanol, ethanol, chloroform, N-methylpyrrolidone and the like.
Preferably, the hydrothermal reaction temperature in the step 2) is controlled to be 120-200 ℃, and the heat preservation time is 10-24 hours.
Preferably, the pre-oxidation treatment in the muffle furnace in the step 3) is carried out for 1-10 ℃ min-1Heating to 150-350 ℃, and keeping the temperature for 0.5-5 h.
Preferably, the high-temperature pyrolysis treatment in the step 4) is performed at 1-10 ℃ for min-1Heating to 250-400 deg.C, keeping the temperature for 1-3 h, and then heating to 1-10 deg.C for min-1Heating to 600-900 ℃ and preserving the heat for 8-16 h.
Preferably, the protective inert gas for high-temperature pyrolysis in the step 4) is one or more of nitrogen, helium, argon and the like.
The invention provides the silicon-carbon composite cathode material and the preparation method of the silicon-carbon composite cathode material based on the scheme, and the prepared silicon-carbon composite cathode material is used as an electrode material of a lithium ion battery and is expected to be widely applied to the fields of portable electronic products, electric tools, electric automobiles, wind-solar energy storage power stations and the like.
The invention has the beneficial effects that:
1) the surfactant is added to effectively inhibit the agglomeration of the nano silicon particles, and simultaneously, the surfactant can improve the conductivity of the composite material by a carbon layer generated by pyrolysis on the surfaces of the nano silicon particles during high-temperature carbonization treatment, and different surfactants are utilized to pyrolyze carbonThe strength, toughness and other mechanical properties of the composite material restrict, absorb and relieve the volume effect in the process of silicon lithiation/delithiation and stabilize the structure of the three-dimensional porous bird nest composite; preoxidation treatment in air to generate dense SiO on the surface of the silicon nano-particlesxThe binding layer can effectively inhibit the volume expansion of silicon in the lithiation process and reduce the resistance of a passivation layer on the surface of the silicon; the carbon nano tube can effectively accommodate the volume change of silicon in the charging and discharging processes, and the stability of the composite material structure is kept; nanometer silica powder and SiOxThe layer, the carbon nano tube and the carbon layer formed by surfactant pyrolytic carbon jointly construct a three-dimensional porous nest-shaped structure in the silicon-carbon composite material;
2) the composite negative electrode material has three-dimensional porous nest-shaped structures, and the porous structures not only can reduce the deformation of the electrode, but also can provide a large contact area between an active substance and an electrolyte and improve the diffusion rate of lithium ions, thereby further improving the electrochemical performance of the composite electrode;
3) experimental results show that the first charge-discharge specific capacity of the lithium ion battery prepared from the silicon-carbon composite negative electrode material provided by the invention is 1700 mA.h.g-1After 500 cycles, the capacity was maintained at 1750 mA · h · g-1And compared with the initial capacity, the composite material has no attenuation, and has high reversible specific capacity and cycling stability. In addition, the method provided by the invention has the advantages of simple operation, low cost, environmental friendliness and the like.
Description of the drawings:
FIG. 1 is a transmission electron micrograph of a silicon carbon composite prepared in example 1;
FIG. 2 is a voltage-specific capacity plot of the silicon carbon composite prepared in example 1;
FIG. 3 is a specific capacity-cycle number curve for the silicon carbon composite prepared in example 1;
FIG. 4 is a specific capacity-cycle number curve for the silicon carbon composite prepared in example 2;
FIG. 5 is a voltage-specific capacity curve of the nano-silicon powder electrode of comparative example 1;
FIG. 6 is a specific capacity-cycle number curve of the nano silicon powder electrode of comparative example 1.
The specific implementation mode is as follows:
embodiments of the present invention will be described in detail below with reference to specific examples. The following examples are only preferred embodiments of the present invention to facilitate better understanding of the present invention and therefore should not be construed as limiting the scope of the present invention. Various modifications and changes may be made by those skilled in the art, and any modification, equivalent replacement or improvement made without departing from the spirit and principle of the present invention should be covered within the protection scope of the present invention.
Example 1:
1. preparation of silicon-carbon composite material
(1) Adding 1.0 g of polyoxyethylene type nonionic surfactant fatty acid polyoxyethylene ester and 1.0 g of quaternary ammonium salt type cationic surfactant octadecyl trimethyl ammonium chloride into a 500 mL round-bottom flask containing 200 mL of ethanol, adding 0.8 g of nano silicon powder, stirring and ultrasonically treating for 30 minutes, adding 0.5 g of carbon nano tube, continuously stirring and ultrasonically treating for 2 hours, and transferring the solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours;
(2) after the hydrothermal reaction is finished, carrying out reduced pressure rotary evaporation, drying the obtained solid in a 60 ℃ oven for 2 h, then putting the dried solid in a muffle furnace for preoxidation treatment at 250 ℃ for 2 h, then putting the preoxidized sample in a nitrogen-filled tube furnace for sintering treatment, raising the temperature to 700 ℃ after sintering at 300 ℃ for 2 h, sintering for 12 h, taking out the sintered sample, and grinding to obtain the silicon-carbon composite material;
(3) the obtained silicon-carbon composite material was analyzed by a transmission electron microscope, and the results are shown in fig. 1.
2. Preparation of silicon-carbon composite material cathode
According to the active material (silicon carbon composite): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
3. preparation and testing of lithium ion batteries
And placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. The electrolyte is 1 mol.L-1Lithium hexafluorophosphate (LiPF)6) The solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, the diaphragm is a polyethylene/propylene composite microporous membrane, and the charge-discharge voltage range is 0.01-1.5V vs. Li+The specific discharge capacity of the half-cell is 1718 mA.h.g-1The specific discharge capacity after 500 cycles is maintained at 1750 mA.h.g-1There is no capacity fade compared to the initial capacity.
Example 2:
1. preparation of silicon-carbon composite material
(1) Adding 2.0 g of sulfonate anionic surfactant sodium dodecyl benzene sulfonate into a 500 mL round-bottom flask containing 200 mL of ethanol, adding 0.8 g of nano silicon powder, stirring and ultrasonically treating for 30 minutes, adding 0.5 g of carbon nano tube, continuously stirring and ultrasonically treating for 2 hours, and transferring the solution into a reaction kettle for hydrothermal reaction at 200 ℃ for 10 hours;
(2) and (3) after the hydrothermal reaction is finished, carrying out reduced pressure rotary evaporation, drying the obtained solid in an oven at 60 ℃ for 2 h, then placing the dried solid in a muffle furnace for pre-oxidation treatment at 320 ℃ for 4 h, then placing the pre-oxidized sample in a tubular furnace through which nitrogen is introduced for sintering treatment, raising the temperature to 900 ℃ for sintering for 16 h after sintering at 300 ℃ for 2 h, taking out the sintered sample, and grinding to obtain the silicon-carbon composite material.
2. Preparation of silicon-carbon composite material cathode
According to the active material (silicon carbon composite): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into wafers with the diameter of 12 mm by a sheet punching machine, drying and weighing the wafers at 120 ℃ for 3 hours, finally pressing the wafers onto a current collector (nickel screen) to obtain an electrode plate, and continuously drying the electrode plate at 120 ℃ for 5 hours for later use.
3. Preparation and testing of lithium ion batteries
And placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. The electrolyte is 1 mol.L-1Lithium hexafluorophosphate (LiPF)6) The solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, the diaphragm is a polyethylene/propylene composite microporous membrane, and the charge-discharge voltage range is 0.01-1.5V vs. Li+Li, tested at 0.1C rate, the specific capacity-cycle number of the half-cell is shown in figure 4, and the first discharge specific capacity of the half-cell is 2893 mA.h.g-1The capacity is kept at 1736 mA · h · g after 120 cycles of circulation-1The capacity retention rate was 60%.
Comparative example 1:
(1) according to the active substance (nano silicon powder): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
(2) and placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. The electrolyte is 1 mol.L-1Lithium hexafluorophosphate(LiPF6) The solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, the diaphragm is a polyethylene/propylene composite microporous membrane, and the charge-discharge voltage range is 0.01-1.5V vs. Li+The specific discharge capacity of the half-cell is 719 mA.h.g.for the first time-1The capacity of the nanometer silicon powder electrode is attenuated very quickly and can only be kept at 30 mA.h.g finally-1
The first discharge specific capacity of the three-dimensional porous nest-shaped silicon-carbon composite negative electrode material provided by the invention is higher than that of a nano silicon powder electrode, and the capacity can still be maintained at 1700 mA.h.g after 100 cycles-1The cycle performance is obviously superior to that of a nanometer silicon powder electrode, which shows that the three-dimensional porous nest-shaped silicon-carbon composite negative electrode material provided by the invention has the advantages of high specific capacity and good cycle performance.

Claims (8)

1. The three-dimensional porous nest-shaped silicon-carbon composite negative electrode material is characterized by having a structural form related to a preparation method, and comprising nano silicon powder and SiOxA layer, carbon nanotubes, and a carbon shell formed by surfactant pyrolytic carbon; the silicon-carbon composite material contains 15-50 wt% of silicon and SiOxThe content of (1-10 wt.%), the content of carbon nano tube is 5-30 wt.%, and the content of surfactant pyrolytic carbon is 1-30 wt.%;
the three-dimensional porous nest-shaped silicon-carbon composite negative electrode material is prepared by the following synthesis steps:
1) silicon/carbon nanotube/surfactant pretreatment: dispersing a surfactant in a solvent, adding nano silicon powder and carbon nano tubes, and carrying out ultrasonic stirring treatment to obtain a uniformly dispersed mixed solution;
2) preparation of silicon/carbon nanotube/surfactant precursor: transferring the mixed solution obtained by the treatment in the step 1) into a reaction kettle for hydrothermal reaction treatment;
3) silicon/SiOxPreparation of carbon nanotube/surfactant precursor: separating the solvent from the silicon/carbon nanotube/surfactant precursor obtained by the step 2) by using a rotary evaporator, and carrying out pre-oxidation treatment in a muffle furnace;
4) silicon/SiOxPreparing a/carbon nano tube/carbon composite negative electrode material: silicon/SiO treated by the step 3)xAnd pyrolyzing the carbon nanotube/surfactant precursor at high temperature under the protection of inert gas in a tube furnace.
2. The three-dimensional porous nest-shaped silicon-carbon composite negative electrode material as claimed in claim 1, characterized in that the surfactant is one or more of carboxylate type, sulfate type, sulfonate type and phosphate type anionic surfactants, amine salt type, quaternary ammonium salt type and heterocyclic type cationic surfactants, amino acid type and betaine type zwitterionic surfactants or polyoxyethylene type and polyhydric alcohol type nonionic surfactants.
3. The three-dimensional porous nest-shaped silicon-carbon composite anode material as claimed in claim 1, wherein the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, the typical tube diameter is 1-100 nm, and the aspect ratio is 1000: 1 or more.
4. The three-dimensional porous nest-shaped silicon-carbon composite anode material as claimed in claim 1, wherein the nano silicon powder has a particle size distribution within a range of 30-500 nm.
5. The three-dimensional porous nest-shaped silicon-carbon composite anode material is characterized in that the solvent is one or more of deionized water, methanol, ethanol, chloroform and N-methylpyrrolidone.
6. The three-dimensional porous nest-shaped silicon-carbon composite anode material according to claim 1, characterized in that the hydrothermal reaction temperature is controlled to be 120-200 ℃, and the holding time is 10-24 h.
7. The three-dimensional porous nest-shaped silicon-carbon composite negative electrode material of claim 1, characterized in that the pre-oxidation treatment is carried out in a muffle furnace at 1-10 ℃ for min-1Heating to 150-350 ℃, and keeping the temperature for 0.5-5 h.
8. The three-dimensional porous nest-shaped silicon-carbon composite negative electrode material as claimed in claim 1, wherein the high-temperature pyrolysis treatment is performed at 1-10 ℃ for min-1Heating to 250-400 deg.C, keeping the temperature for 1-3 h, and then heating to 1-10 deg.C for min-1Heating to 600-900 ℃ and preserving the heat for 8-16 h.
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